EP0691996A4 - Composition de resine polyamide - Google Patents

Composition de resine polyamide

Info

Publication number
EP0691996A4
EP0691996A4 EP93909571A EP93909571A EP0691996A4 EP 0691996 A4 EP0691996 A4 EP 0691996A4 EP 93909571 A EP93909571 A EP 93909571A EP 93909571 A EP93909571 A EP 93909571A EP 0691996 A4 EP0691996 A4 EP 0691996A4
Authority
EP
European Patent Office
Prior art keywords
polyamide resin
glass fibers
glass
resin composition
examples
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93909571A
Other languages
German (de)
English (en)
Other versions
EP0691996A1 (fr
Inventor
Ryuichi Hayashi
Masahiro Nozaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0691996A1 publication Critical patent/EP0691996A1/fr
Publication of EP0691996A4 publication Critical patent/EP0691996A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass

Definitions

  • the present invention relates to a polyamide resin composition
  • a polyamide resin composition comprising a polyamide resin and a reinforcing filler, such as glass fibers, glass flakes, or mineral fillers, said composition exhibiting good flow and moldability and providing a high precision molded article with a smooth surface and low warpage, while maintaining high stiffness and high strength.
  • Fiber reinforcing agents such as glass fibers, have heretofore been mixed with polyamide resins for reinforcing the resins.
  • the present invention aims to provide a polyamide resin composition capable of being molded into a high precision molded article with good stiffness, good strength, and low warpage and further capable of being molded by a conventional injection molding machine into a molded article with complicated and fine parts, or into a large-sized part, as well as being capable of generating a molded article with a smooth surface appearance.
  • a polyamide resin composition comprising 30-50 parts by weight of a polyamide resin and 70-50 parts by weight of a combination of glass fibers and glass flakes or mineral filler, said resin composition having a melt viscosity when molding, at a shear rate of 1,216 sec- 1 , of 50-200 Pascal seconds.
  • a polyamide resin composition comprising 30-50 parts by weight of polyamide resin and 70-50 parts by weight of glass flakes, said resin composition having a melt viscosity when molding, at a shear rate of 1,216 sec -1 , of 50-200 Pascal seconds.
  • the above objectives were also met by a polyamide resin composition comprising 40-50 parts by weight of polyamide resin and 60-50 parts by weight of a mineral filler, said resin composition having a melt viscosity when molding, at a shear rate of 1,216 sec" 1 , of 50-200 Pascal seconds.
  • the measures to be regulated so as to strike a good balance between the moldability of the resin, and the strength and appearance of molded articles made from the polyamide resin composition are as follows: (1) the mixing ratio of the polyamide resin and the reinforcing agent and (2) the melt viscosity of the polyamide resin composition at a shear rate of 1,216 sec -1 . Limiting the above two items to specific ranges, and further employing glass flakes or mineral fillers as reinforcement agents, can provide simultaneously the excellent moldability and high strength of molded articles together with a favorable surface appearance and low wa ⁇ age, of said articles.
  • Melt viscosity means a viscosity measured under a shear rate of 1,216 sec -1 at the resin temperature during the molding of an absolutely dry molded article obtained from the polyamide resin composition.
  • the viscosity can be, for example, measured by a Kayness capillary viscometer.
  • the resin temperature during molding is about 280°C for a composition using nylon 66 as a polyamide resin.
  • a polyamide resin composition having a melt viscosity, when molding, of less than 50 Pascal seconds, at a shear rate of 1,216 sec -1 is not preferred because of problematic moldability behavior.
  • Such a resin composition is considered to have a low melt viscosity, which results in the formation of a burr or a dripping resin composition (the so-called "running nose phenomenon").
  • a melt viscosity during molding exceeding 200 Pascal seconds, at a shear rate of 1,216 sec- 1 is not preferred in that a resin composition such as those of this invention with at least 50% by weight of fillers, such as a glass flakes, mineral filler, or glass fibers, will have phenomena such as poor appearance due to the glass flakes, and the like, rising to the surface of the molded article, as well as requiring a high injection pressure because thin wall sections during injection molding tend to fail to be filled by the resin composition.
  • polyamide resin composition of this invention it is preferred to mold the polyamide resin composition of this invention by injection molding a preparation so as to exhibit a resin melt viscosity at a resin temperature during injection molding (normally 15-40°C higher than the melting point) of 50-200 Pascal seconds at a shear rate of 1,216 sec 1 .
  • the polyamide resin composition of this invention comprises a matrix polyamide resin which is filled with certain reinforcing materials, such as glass fibers, glass flakes, or mineral fillers, singly or in combination.
  • the type of reinforcing material used is selected depending upon the desired physical properties of the molded articles in terms of stiffness, strength, and the like, as well as the extent of allowable wa ⁇ age of the molded articles. Although it depends upon the type of glass flakes or mineral fillers used, in general, the greater the amount of glass flakes or mineral fillers used for filling, the less wa ⁇ age and the higher precision of the molded articles, while at the same time, these more favorable types are provided with a delustered surface appearance.
  • the amounts of the reinforcing materials mixed with the polyamide resin are expressed on the basis of the total weight of the polyamide resin and these reinforcing materials, Specifically in terms of parts by weight per 100 parts by weight of the total weight of the polyamide resin and reinforcing material. If the reinforcing material is a combination of glass fibers and glass flakes or if it is a combination of glass fibers and mineral fillers, or if it uses only glass flakes, then 50-70 parts by weight of these reinforcing materials are mixed with the complementary amount of polyamide resin, 50-30 parts by weight.
  • mineral fillers are used by themselves, 50-60 parts by weight of the mineral fillers are mixed with a complementary amount of the polyamide resin, 50-40 parts by weight. If the amount of reinforcing material inco ⁇ orated is greater than that defined here, the resultant resin composition will have reduced flow and reduced moldability, such as processability, and the like, and at the same time will experience difficulty in achieving a uniform mixed dispersion state, as well as ending up with a deteriorated surface condition for the molded article. Decreasing the amount of reinforcing material to be mixed to less than the range defined herein, will result in the molded article having insufficient mechanical strength.
  • the polyamide resin used as a matrix in this invention is preferably a low viscosity-type.
  • the resin is a low viscosity-type polyamide having a melt viscosity of not more than 80 Pascal seconds when tested absolutely dry at an injection molding resin temperature (normally 15-40°C higher than the melting point) and at a rate of 1,216 sec 1 .
  • Such a low viscosity polyamide resin can be prepared by molecular weight control during polymerization, for example, by generating a low molecular weight polyamide by controlling water during polymerization or by blending a high molecular weight polyamide with a low molecular weight polyamide. The mixing may be achieved by mixing pellets or mixing in the molten state.
  • a polyamide resin with lower melt viscosity will be able to wet the surface of the glass fibers, and the like, so that the resultant polyamide resin composition will show improved processability and moldability, as well as prevent the filled glass fibers, and the like, from rising to the surface of the molded articles.
  • polyamide in this invention is meant a linear synthetic polymer having amide-linkages in the main chain obtained by a polycondensation reaction of a diamine and a dibasic acid, ring opening polymerization of lactam, or polycondensation of an amino carboxylic acid (for example, nylon 6, nylon 66, nylon 68, nylon 610, nylon 612, or the like) or nylon copolymers of these components, also including aromatic polyamides.
  • the glass fibers used in this invention are those normally used as a reinforcing materials, including any shape, long and short fiber glasses. Depending upon the glass fiber length, compounding by an extruder will require considering the correct design for the screw or using a downstream system.
  • the glass flakes used in this invention are preferably about 1 um to 8 um thick and not more than 1700 um in particle size. It is preferred to give a suitable treatment on the surface of the glass flakes, such as a silane treatment, or the like, so as to increase the adhesion with the polyamide resin.
  • a suitable treatment on the surface of the glass flakes such as a silane treatment, or the like, so as to increase the adhesion with the polyamide resin.
  • the particle size and particle size distribution should be accommodated by controlling the process conditions in compounding by an extruder or considering the optimum screw design, and the like.
  • the mineral fillers used in this invention include, for example, an Si0 2 -MgO type such as talc, an Si0 2 -CaO type, such as wollastonite (calcium silicate), an Si0 2 -Al 2 0 3 type, such as kaolin, an Si0 2 -Al 2 0 3 -K 2 0 type, such as mica, as well as calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium oxide, and the like.
  • talc, wollastonite, kaolin, mica, and the like are silane surface-treated.
  • the mineral fillers are preferably kaolin clay having a particle size of about 0.3-20 um which are also surface-treated with an amino silane, and the like. Glass beads can also be used in a similar manner to the glass flakes or mineral fillers.
  • the glass beads which can be used are spherical with a diameter of about 10-100 um including ordinary glass beads having a surface treatment or similar hollow glass beads, and the like
  • the polyamide resin composition of this invention in addition to the above polyamide resin, glass fibers, glass flakes, or mineral fillers, may optionally be mixed with one or more usual additives, such as stabilizers against oxidation, heat, and ultraviolet light degradation or inhibitors thereof; lubricants, and mold release agents; colorants, including dyes and pigments; nucleating agents; blowing agents; plasticizers; inorganic fillers; flame retarders; antistatic agents; and the like.
  • additives such as stabilizers against oxidation, heat, and ultraviolet light degradation or inhibitors thereof; lubricants, and mold release agents; colorants, including dyes and pigments; nucleating agents; blowing agents; plasticizers; inorganic fillers; flame retarders; antistatic agents; and the like.
  • Nylon 66 having a suitable molecular weight or a blend of nylon 66 and nylon 6 was melt mixed with commercial chopped strand short glass fibers, 10 microns in diameter and 3 mm long, as a glass fiber component, in a twin screw extruder having optimally designed screws. In order to bring the resin melt temperature to 280-300°C, the extruder barrel temperature and screw revolution rate were adjusted. In a similar manner, a silane-treated kaolin clay as a mineral filler component was melt mixed with nylon 66 or a blend of nylons 66 and 6.
  • the resultant resin pellets were injection molded as described below in order to evaluate moldability and to measure these molded articles in terms of wa ⁇ age, surface condition, and dynamic properties. These resin pellets were each dried in dry air at 80°C prior to molding.
  • Moldability was evaluated by injection molding the resin pellets into box-like parts having dimensions 45 cm x 19 cm x 8 cm. Moldability was evaluated in terms of the pressure needed for molding, the ease of filling into a mold, conditions of molding machine barrels, "running nose” phenomenon in the nozzle section, etc. to give a rating of excellent, good, fair, or poor. The surface state, such as the surface roughness and wa ⁇ age, of these molded articles, was visually inspected and given one of the ratings mentioned above.
  • Mold shrinkage was determined from 3 inch x 5 inch x 1/8 inch sheets molded from the resin pellets.
  • the physical properties for the resin pellets was determined by injection molding, on a 6 oz. injection molding machine, the pellets into test pieces having dimensions 13 mm x 130 mm x 3.2 mm.
  • the reaction time was 5-6 minutes
  • the barrel temperature was 270-280°C
  • the nozzle temperature was 280-290°C.
  • the mold temperature was about 90°C so as to carry out a molding cycle of 10/20 or 20/20 cycles (ram forward in seconds/retention in seconds).
  • the resultant molded articles were tested for their physical properties immediately after molding, as well as at 150°C. Molding and testing was done in accordance with ASTM D638.
  • the resin melt viscosity of the above molded articles was measured using a Toyo Seiki capillograph viscometer for an absolutely dry molded article (containing 0.1-0.15% water) at 280°C at a shear rate of 1,216 sec 1 .
  • Resin pellets were formed from the extruded resin. Molded articles were injection molded in a manner similar to that of Example 1 from these resin pellets to measure moldability, the surface appearance, wa ⁇ age, and physical properties of the molded articles.
  • the samples of Examples 11, 12, 16, and 17 were molded into sheets with a ribbed structure 400 mm x 100 mm x 10 mm to measure their wa ⁇ age. The results are summarized in Table 2 and Figures 2 and 3.
  • Examples 1-6 and Example 9 containing mineral fillers and glass fibers showed significantly higher flexural modulus, flexural strength, and tensile strength than Control Example 4.
  • a comparison of Control Example 1 with Examples 1-9 shows that the use of glass fibers alone gave high stiffness and strength; however, there was some room for improvement in the areas of moldability, molded goods' surface appearance, and molded goods' wa ⁇ age, whose deficiency can be improved upon by the combined use of mineral fillers with the glass fibers.
  • Control Example 2 which had too high a melt viscosity showed a resin filling which was unsatisfactory under the usual injection molding conditions, giving molded articles that had considerably poor surface appearance.
  • Control Example 3 which had too low a resin viscosity, resulted in extensive resin "nose running", thereby making molding difficult.
  • Example 10 containing only 60% mineral fillers had inferior tensile strength to that of Control Example 5, but had a higher modulus and better moldability, surface properties, and wa ⁇ age.
  • the amount of wa ⁇ age of sheets having a ribbed structure, as shown in Figure 1, was smaller with Examples 2 and 9, containing 15 and 45%, 45% and 15%, of mineral fillers and glass fibers, respectively, compared to Control Example 1 containing 60% of glass fibers alone.
  • Examples 11-16 containing both glass flakes and glass fibers compared to Control Example 4 containing no glass flakes, exhibited considerably higher flexural moduli and strengths, as well as tensile strengths, while exhibiting similarly good moldability, surface properties, and low wa ⁇ age.
  • the low wa ⁇ age behavior of Examples 11-18 is also evident in their low molding shrinkage and a shrink ratio close to 1 (smaller anisotropy in shrinkage) with better results having a higher glass flake content for preventing wa ⁇ age.
  • Examples 17 and 18, containing 60% and 70%, respectively, of glass flakes alone show essentially no anisotropy in shrinkage, giving a good low wa ⁇ age molded article which is also provided with a high flexural modulus.
  • Examples 11-16, particularly Examples 13, 14, and 15 showed less anisotropic molding shrinkage, as well as a similar high flexural modulus, thereby providing a low wa ⁇ age, high stiffness molded article.
  • Figures 2 and 3 further specifically compare wa ⁇ age based on
  • Example 11 At total weights of glass flakes and glass fibers held constant at 16%, Examples 11, 12, 16, and 17 demonstrate decreasing wa ⁇ age with an increase in glass flakes content, compared to Control Example 1, which contained 60% of the glass fibers alone. In particular, Example 17, containing 60% of glass flakes alone, gave an essentially wa ⁇ age-free good molded article, which was also provided with high stiffness.
  • Example 11 shows that the combination of glass flakes and glass fibers gave even lower wa ⁇ age and higher physical properties, specifically in terms of tensile strength and notched Izod impact strength, compared to combinations of mineral fillers and glass fibers.
  • Control Example 4 had good moldability, but Control Examples 2 and 7 having increased levels of reinforcing agents showed too high a viscosity, although Control Example 4 had 38% reinforcing agent and Control Examples 2 and 7 had 60% reinforcing agent and are based on the same nylon 66. This suggests that merely increasing the levels of reinforcing agents degrades the flow and that it is important to adjust the melt viscosity of the polyamide resin composition.
  • FIGURES Figure 1 This is a diagram showing the state of wa ⁇ age of the molded articles from the polyamide resin compositions of Control Example 1 and Examples 2 and 9.
  • Figure 2 This is a diagram showing the state of wa ⁇ age of the molded articles from the polyamide resin compositions of Examples 11, 12, and 16.
  • Figure 3 This is a diagram showing the state of wa ⁇ age of the molded articles from the polyamide resin compositions of Example 17 and Control Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine polyamide contenant 30 à 50 parties en poids de résine polyamide et 70 à 50 parties en poids d'une combinaison de fibres de verre et de flocons de verre. Sa viscosité à l'état fondu au moment du moulage est de 50-200 pascal secondes à une vitesse de cisaillement de 1,216 sec-1. Le gauchissement d'articles réalisés par moulage à partir de compositions de résine polyamide de l'exemple 17 et de l'exemple de référence 1 est représenté sur le diagramme annexé.
EP93909571A 1993-03-29 1993-03-29 Composition de resine polyamide Withdrawn EP0691996A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1993/002906 WO1994022942A1 (fr) 1993-03-29 1993-03-29 Composition de resine polyamide

Publications (2)

Publication Number Publication Date
EP0691996A1 EP0691996A1 (fr) 1996-01-17
EP0691996A4 true EP0691996A4 (fr) 1997-06-18

Family

ID=22236459

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93909571A Withdrawn EP0691996A4 (fr) 1993-03-29 1993-03-29 Composition de resine polyamide

Country Status (2)

Country Link
EP (1) EP0691996A4 (fr)
WO (1) WO1994022942A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080119603A1 (en) * 2006-11-22 2008-05-22 Georgios Topoulos Mobile telephone housing comprising polyamide resin composition
US8853324B2 (en) * 2006-11-22 2014-10-07 E I Du Pont De Nemours And Company Mobile telephone housing comprising polyamide resin composition
FR2922553B1 (fr) 2007-10-19 2009-12-18 Rhodia Operations Composition polymere thermoplastique a base de polyamide
EP2924065A1 (fr) * 2014-03-26 2015-09-30 LANXESS Deutschland GmbH Compositions de polyamide
EP2924068A1 (fr) * 2014-03-26 2015-09-30 LANXESS Deutschland GmbH Compositions de polyamide
DE202014008607U1 (de) * 2014-10-31 2014-11-24 Lanxess Deutschland Gmbh Polyamidzusammensetzungen
US20180371207A1 (en) * 2015-12-15 2018-12-27 Imerys Usa, Inc. Polymer composite compositions including hydrous kaolin
WO2018039454A1 (fr) * 2016-08-26 2018-03-01 Imerys Usa,Inc. Compositions composites polymères comprenant du kaolin
EP3725833B1 (fr) 2019-04-16 2021-03-17 Ems-Chemie Ag Matière thermoplastique de moulage renforcé

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JPS5896651A (ja) * 1981-12-02 1983-06-08 Showa Denko Kk ポリアミド樹脂組成物
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JPS61254662A (ja) * 1985-05-07 1986-11-12 Seiko Epson Corp 樹脂組成物
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JPS63168454A (ja) * 1986-12-29 1988-07-12 Ube Ind Ltd エンジン周り部品用ポリアミド樹脂組成物
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JPH01176555A (ja) * 1988-01-06 1989-07-12 Mitsubishi Kasei Corp 積層ブロー成形品
JPH01263151A (ja) * 1988-04-15 1989-10-19 Mitsubishi Gas Chem Co Inc 自動車用ミラーステイ
EP0423510A1 (fr) * 1989-10-20 1991-04-24 General Electric Company Matières à mouler thermoplastiques à haute densité
EP0553617A1 (fr) * 1992-01-25 1993-08-04 BASF Aktiengesellschaft Procédé pour préparer des compositions de moulage thermoplastiques contenant de agents de charge
FR2692902A1 (fr) * 1992-06-25 1993-12-31 Asahi Chemical Ind Composition à base de résine de polyamide et objets moulés en cette composition.

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JPS57168941A (en) * 1981-04-13 1982-10-18 Toray Ind Inc Heat-resistant reinforced polyamide molding
JPS5896651A (ja) * 1981-12-02 1983-06-08 Showa Denko Kk ポリアミド樹脂組成物
JPS59165403A (ja) * 1983-03-10 1984-09-18 Matsushita Electric Ind Co Ltd 樹脂マグネツト組成物
JPS61254662A (ja) * 1985-05-07 1986-11-12 Seiko Epson Corp 樹脂組成物
JPS61278561A (ja) * 1985-06-04 1986-12-09 Ube Ind Ltd ガラス短繊維入りポリアミド組成物およびメツキ成形体
JPS62116660A (ja) * 1985-11-15 1987-05-28 Daiseru Hiyurusu Kk 強化ポリアミド樹脂組成物
JPS62121725A (ja) * 1985-11-21 1987-06-03 Mitsubishi Monsanto Chem Co アミド系樹脂成形品の製造方法
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JPS62246958A (ja) * 1986-04-21 1987-10-28 Asahi Chem Ind Co Ltd ポリアミド系車輛用部材
JPS638417A (ja) * 1986-06-27 1988-01-14 Mitsubishi Monsanto Chem Co アミド系樹脂成形品
JPS63168454A (ja) * 1986-12-29 1988-07-12 Ube Ind Ltd エンジン周り部品用ポリアミド樹脂組成物
JPS63205351A (ja) * 1987-02-20 1988-08-24 Ube Ind Ltd 強化ポリアミド組成物
JPH01176555A (ja) * 1988-01-06 1989-07-12 Mitsubishi Kasei Corp 積層ブロー成形品
JPH01263151A (ja) * 1988-04-15 1989-10-19 Mitsubishi Gas Chem Co Inc 自動車用ミラーステイ
EP0423510A1 (fr) * 1989-10-20 1991-04-24 General Electric Company Matières à mouler thermoplastiques à haute densité
EP0553617A1 (fr) * 1992-01-25 1993-08-04 BASF Aktiengesellschaft Procédé pour préparer des compositions de moulage thermoplastiques contenant de agents de charge
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See also references of WO9422942A1 *

Also Published As

Publication number Publication date
EP0691996A1 (fr) 1996-01-17
WO1994022942A1 (fr) 1994-10-13

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